Monoazo dyes



United States Patent 3,142,669 MONOAZO DYES James F. Feeman, Wyomissing,Pa., assignor to Crompton 8; Knowles Corporation, Worcester, Mass, acorporation of Massachusetts No Drawing. Filed Dec. 12, 1960, Ser. No.75,112 4 Claims. (Cl. 260-199) This invention relates to a new group oforganic compounds which are useful as dyes. The new compounds have thefollowing structure:

SIO3H HQN (Structure 1) wherein R is a radical selected from the groupconsisting of aliphatic, alicyclic, aromatic and heterocyclic organicacyl radicals which are devoid of water-solubilizing ionogenic groups,and have molecular weights in the range of from 70 to 190; and triazinylradicals having the structure III

wherein X and Y represent substituents selected from the groupconsisting of --Cl, Olower alkyl, NH NHlower alkyl, or -N(lower alkyl)and R is a radical selected from the group consisting of O2NR2N=N l rNreducing (Reaction II) the nitro group to the corresponding amine:

S|O H and reacting (Reaction III) the amino group of the thusformedcompound with an acid halide, anhydride, isocyanate, chloroforrnate,cyanuric chloride, etc. which has an appropriate R group to yield theStructure I type compounds.

The compounds prepared in this way have unique and highly valuableproperties when used as dyes. They "ice Will dye polyurethan fibers andnatural and synthetic polyamide fibers such as nylon, silk and wool, inpure lightfast red and scarlet shades; and washfastness can be enhancedby conventional aftertreatments. The dyeing can be from neutral solutionand with very high degree of dye exhaustion. Because of the neutraldyeing capability, the compounds of this invention can be used in mixedbaths with direct dyes, and mixed fabrics, formed of cellulosic fiberand polyarnide or polyurethane fiber, can be dyed in a single bath.

Nitroanilines and nitroaniline derivatives which can be diazotized andcoupled with gamma acid to introduce suitable R radicals includemeta-nitroaniline, paranitroaniline, 2-amino-4-nitrotoluene,2-arnino-5-nitrotoluene, 2-amino-4-nitroanisole, Z-amino-S-nitroanisole,and the like. The meta compounds are used for producing the scarletshades and the para compounds are used for producing the reds.

In general, as to the radicals forming the R grouping in the Structure Icompound, it is preferred to employ any radical which is sufficientlysmall, from a standpoint of size or bulk, to enable the Structure Icompounds to dissolve in substantially neutral aqueous solutions. The Rand R radicals should not include any water solubilizing ionogenicgroups such as SO H, -COOH, SO NH etc. because such groups impart excesssolubility which interferes with the desired neutral drying capability.

As R radicals, it is preferred to employ the aliphatic, alicyclic,aromatic and heterocyclic organic acyl radicals having molecular weightsin the range of from about 70 to 190. Where the molecular weight of theR group is greater than about 190, the Structure I compound tends tobecome too water insoluble to function as a dye. Where the molecularweight of the R group is less than about 70, the solubilitycharacteristics become such that the Structure I compound cannot be usedfor dyeing under substantially neutral pH conditions.

Structure II compounds are those in which acid chlorides are employed inReaction III to form:

s oan HO O H HiN wherein R is selected from the group consisting ofalkyl, halogenated alkyl, aryl, cycloalkyl, aralkyl, alkoxyalkyl,chlorinated aryl, nitrated aryl, and mononuclear heterocyclic radicalswhich are devoid of water-solubilizing ionogenic groups, and havemolecular Weights in the range of from 42 to 162; and R is a radicalselected from the group consisting of and their lower alkyl and loweralkoxyl substituted derivatives. Typical acid chlorides which are usefulin introducing R radicals include butyryl chloride, pentanoyl chloride,hexanoyl chloride, heptanoyl chloride, octanoyl chloride, nonanoylchloride, decanoyl chloride, lauroyl chloride, chloroacetyl chloride,Z-chloro-propionyl chloride, toluyl chloride, anisoyl chloride,cyclohexane carboxylic acid chloride, phenylacetyl chloride,phenoxyacetyl chloride, cinnamoyl chloride, bromobenzoyl chloride,fluorobenzoyl chloride, hydrocinnamoyl chloride, naphthoyl chloride,methoxypropionyl chloride, Z-chloro-benzoyl chloride,2,4-dichlorobenzoyl chloride, meta-nitrobenzoyl chloride,para-nitrobenzoyl-chloride, furoyl chloride, and the like.

J Structure III compounds are those in which chloroformates are employedin Reaction III to form:

SO3H

wherein R is selected from the group consisting of alkyl, halogenatedalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, phenoxyalkyl, cycloalkyl, aralky,aryl of the benzene series, alkoxyaryl of the benzene series,chlorinated aryl of the benzene series, alkyl aryl of the benzeneseries, heterocyclic, heterocyclic alkyl radicals which are devoid ofwater-solubilizing ionogenic groups, and have molecular weights in therange from 26 to 146; and R is a radical selected from the groupconsisting of 1 ll 1 R6 N" -NR;N=N

al l wherein R is selected from the group consisting of alkyl, aryl (ofthe benzene and naphthalene series), cycloalkyl, aralkyl, andheterocyclic radicals which are devoid of water-solubilizing ionogenicgroups, and which have molecular weights in the range from 27 to 147;and R is a radical selected from the group consisting of and their loweralkyl and lower alkoxyl' substituted derivatives. Typical isocyanateswhich are useful in introducing R radicals include butyl isocyanate,hexylisocyanate, phenyl isocyanate, tolyl isocyanate, naphthylisocyanate, cyclohexyl isocyanate, benzyl isocyanate, thiazolylisocyanate, and the like.

Structure V compounds are those in which triazines are employed inReaction III to form:

I SO H N wherein X and Y represent substituents selected from the groupconsisting of Cl, O-lower alkyl, NH NHlower alkyl and -N(lower alkyl)and R is a radical selected from the group consisting of and their loweralkyl and lower alkoxy derivatives. The triazinyl radical can begenerated by reacting the aminoazo compounds of Reaction II withcyanuric chloride, cyanuric bromide and the like. If desired, one ormore of the halogens can be replaced with ammonia, methylamine,ethylamine, dimethylamine, diethylamine, and the like.

The availability and cost of intermediates and production economics arepractical limitations which must be considered in building the newcompounds of this invention; and for these reasons compounds having thestruc ture':

SIOsH HzN (Structure VI) wherein R represents one of the followingradicals: phenyl, lower alkyl (i.e. about 3 to 9 carbons) and loweralkoxy (i.e. about 2 to 8 carbons), and R represents one of'thefollowing radicals:

constitute a presently preferred group of compounds of this invention.

The following examples will serve to illustrate how the compounds ofthis invention can be prepared and used. In these examples, unlessotherwise indicated, parts are by weight, temperatures are given indegrees centigrade, and percentages are percentages by weight.

and

Example 1 A's'olution' was prepared in 1000 parts of'water of 35.8 partsof the dye having the structure:

S|O3H zN (prepared by coupling diazotized para-nitroaniline with7-amino-l-naphthol-3-sulfonic acid under acidic conditions, followed byreduction of the nitro group with a suitable reducing agent, such assodium sulfide, in alkaline solution); Five parts of sodium carbonatewas added to the solution at 25. Then 25 parts of benzoyl chloride wasadded with'vigorous stirring during 30 minutes with simultaneousaddition of parts of 10% sodium hydroXide solution at a rate whichmaintained the pH of the reaction mixture at 9.5 to 10.0. When all ofthe benzoyl chloride had reacted, the suspension was heated to 60,filtered, and dried. The product was a red-brown 1 solid having thestructure:

It dyed polyamide fibers, such as nylon, wool and silk, from asubstantially neutral bath with excellent exhaus tion in clear redshades. The dyeing on nylon exhibited excellent light fastness and goodfastness to washing.

Example 2 In Example 1, while otherwise proceeding as described,para-nitroaniline was replaced with meta-nitroaniline, resulting information of the new compound of the formula:

SOaH

H O I O It was a red solid which dyed nylon, wool and silk, as well asother polyamide fibers, from substantially neutral baths, with excellentexhaustion of the color, in bright scarlet shades having very goodfastness to light and washing.

Example 3 In Example 1, while otherwise proceeding as described, the 25parts of benzoyl chloride was replaced with 25 parts of butylchloroformate, resulting in formation of the new compound of theformula:

SOsH

HO- i r CHs-CHz-CHz-CHr-O-JJ- ON=N It was a red solid, which dyedpolyamide fibers, such as nylon, from substantially neutral baths withexcellent exhaustion in bright scarlet-red shades, having very goodfastness to light and washing.

Example 4 A solution was prepared in 1000 parts of water of 37.2 partsof the dye having the structure:

SOaH

(prepared by coupling diazotized 2-amino-5-nitrotoluene with7-amin0-l-naphth0l-3-sulfonic acid under acidic conditions, andsubsequently reducing the nitro group with a suitable reagent such assodium sulfide in alkaline solution). Sodium carbonate (5 parts) wasadded at 25. Then 25 parts of benzoyl chloride was added with vigorousstirring during 30 minutes with simultaneous addition of 100 parts of10% sodium hydroxide solution at a rate which maintained the pH of thereaction mixture at 9.5 to 10.0. When all the benzoyl chloride hadreacted, the suspension was heated to 60, filtered and dried. Theproduct was a red-brown solid having the structure:

SIO H HO i i C H: HEN

It dyed nylon from a neutral bath in bluish-red shades with excellentexhaustion of the color, and the dyeing exhibited very good fastness tolight and washing.

6 Example 5 A solution was prepared in 1000 parts of water of 38.8 partsof the dye having the structure:

O 0 Ha zN (prepared by coupling diazotized 2-amino-5-nitroanisole with7-amino-1-naphthol-3-sulfonic acid under acidic conditions, andsubsequently reducing the nitro group with a suitable reducing reagent,such as sodium sulfide, in alkaline solution). Sodium carbonate (5parts) was added at 25. Then 25 parts of benzoyl chloride was added withvigorous stirring during 30 minutes with simultaneous addition of partsof 10% sodium hydroxide solution at a rate which maintained the pH ofthe reaction mixture at 9.5 to 10.0. When all the benzoyl chloride hadreacted, the suspension was heated to 60, filtered and dried. Theproduct was a red solid having the structure:

l l N:;

O 0 Ha HzN Ex- Shade on ample R Precursor R Precursor Nylon NumberButyryl Chloride meta-nitroaniline Scarlet. Hexanoyl Chlori e Do.

Oetanoyl Chlorideo-Chlorobenzoyl Chlorid m-Nitrobenzoyl Chloride-Cinnamoyl Chloride Butyryl Chloride Lauroyl Chloride o-ChlorobenzoylChloride.-. 2,4- Diehlorobenzoyl Chl0 rlde. m-Nitrobenzoyl Chloridep-Nitrobenzoyl Chloride Cinnamoyl Chloride Phenylacetyl ChloridePhenoxyacetyl Chloride Phenyl Iso cyanate.

Ethyl Chloroformate Isopropyl Chloroformate Isoamyl Chloroformaten-Hexyl Chloroforrnate 2-Chloropropionyl Chlor e Cyanurie Chloride (1)Oyanuric Chloride, (2)

Ammonia. Benzoyl Chloride 2-amino-4-nitro- Do.

toluene.

Formulas of representative dyes of the tabulated examples are asfollows:

'7 1 r 8 Example 8 Example 32 I 17TH: S0311 Ho- 4 5 5 A H a( Ha)aCN N=N1 r HQN N- N=N N 2 ilN Example 11' 803E I clzum: 2 1 1. The compound:

o 1 HO SOQH C OH=C H23N- N=N 15 H O Example 22 '1 503B Hm f 2. Thecompound: 1

HO 0 3. Thecompound:

- I SIOaH EN 35 Example 25 O H Ho H zN OCH N ON=N 4. The compound:

I HIN SOaH Example 29' I SOQH HO 1 1 HO- 6N- N=N 1? fGH1-'-(OHa)a'-OC-N'C N=N 11219 I 50 HnN Example 30 References Cited mthe file of H115 patent 11 UNITED STATES PATENTS V 7' 1,1 23 ,430 Tro'ppJan. 5, 1915 O H HO 7 1,201,544 Bergdolt Oct. 17, 1916 H 1,359,969Montmollin Nov. 23, 1920 Q Z C 1,408,405 Schoner et a1. Feb. 28, 19222,374,157 Kvalne's Apr. 17, 1945 HEN 2,374,158 Knight et'al'. Apr. 17,1945 Example 31 2,849,437 Montmollin et a1. Aug. 26, 1958 01 Slo n2,891,941 Fasciati et a1. June 23, 1959 1 N N o FOREIGN PATENTS H 2291,963 Germany May 13, 1916 1- -NC 520,239 Germany Mar. 16, 1931609,117 Germany Feb. 7, 1935 a 1,228,834 France Mar. 21, 1960 UNITEDSTATES PATENT OFFICE" CERTIFICATE OF CORRECTION Patent No. 3,142,669Ju1y.28, 1964 'shown below instead of as in the patent:

C James Feeman It is hereby certified that error appears inthe abovenumbered patent requiring correction and that 'the' said-Letters Patentshould read as corrected below.

Column 1, lines 11 to 18, the formula should appear -as R II\IR N N samecolumn, line 42 for "nitoraniline" read nitroaniline column 3, lines 35to 41., the formula should appear as shown below instead of as in thepatent:

S03H I Signed and sealed this 5th day of January 1965,

(SEAL) Attest:

ERNEST W. SWIDER I I EDWARD J, BRENNER 'Aiztesizing Officer Commissionerof Patents

1. THE COMPOUND: